JPS63311353A - Method for preventing light fading of organic colored substance - Google Patents

Abstract

PURPOSE:To improve the light stability of the org. colored substance of a color photographic sensitive material, etc., by incorporating the org. colored substance in combination with a specified compd., and preventing the decoloration due to light in the color photographic sensitive material. CONSTITUTION:The color photographic sensitive material comprises at least one kind of the org. colored substance in combination with at least one kind of the compd. shown by formula I, thereby improving the light stability of the org. colored substance. In formula I, R<1> is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl or a heterocyclic ring group, Z1 and N2 are each 2 or 3C alkylene chain group. Thus, the discoloration and decoloration of the org. colored substance, especially, a color matter and a dyestuff, etc. used in the color photographic sensitive material are reduced.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for preventing photofading of organic coloring substances, and more specifically, the present invention relates to a method for preventing photofading of organic coloring substances, and more specifically, for example, organic coloring used in the fields of inks, textile dyes, color photography, etc. This invention relates to a method for preventing photobleaching of substances.

[Background of the Invention] It is generally known that organic coloring substances tend to fade due to light. Research is being conducted to prevent such photobleaching of organic coloring substances in the fields of inks, textile dyes, and color photography.

The present invention aims to prevent photofading of such organic coloring substances,
It is used with great advantage.

The organic coloring substance used in the present invention refers to a substance that appears colored to the human eye under sunlight,
Generally 300nm to 800nm in methanol solution
means an organic substance that has at least one absorption maximum in .

Furthermore, in this specification, the term light refers to approximately 300n
This refers to electromagnetic waves of approximately 800nm or less from
UV radiation, visible light from about 400 nm to about 700 nm, and infrared light from about 700 nm to about 800 nm.

There are many reports on methods for improving the light fastness of organic coloring substances, such as pigments or dyes. For example, U.S. Pat. No. 3,432,300 discloses that organic compounds used in color photography, such as indophenol, indoaniline, azo and azomethine dyes, are mixed with phenolic type compounds having fused heterocyclic ring systems.
It is stated that the fastness to visible and ultraviolet light is improved.

In the field of silver halide color photographic materials, dye images obtained from couplers are exposed to light for long periods of time,
It is desirable that the color does not change or fade even when stored under high temperature and high humidity conditions.

However, the fastness of these dye images to mainly ultraviolet rays or visible light is not satisfactory, and it is known that they easily change color and fade when irradiated with these actinic rays. In order to eliminate such drawbacks, conventionally,
Methods have been proposed such as selecting and using various couplers with low fading properties, using ultraviolet absorbers to protect dye images from ultraviolet rays, and introducing groups that impart light resistance into couplers. ing.

However, in order to provide a satisfactory lightfastness to a dye image using, for example, a UV absorber, a relatively large amount of UV absorber is required, in which case the dye image is significantly contaminated due to the coloration of the UV absorber itself. There have been times when I have been rejected. Further, even if an ultraviolet absorber is used, it has no effect on preventing dye images from fading due to visible light, and there are limits to the improvement of light resistance by ultraviolet absorbers. Furthermore, methods using dye image fading inhibitors having a phenolic hydroxyl group or a group that can be hydrolyzed to produce a phenolic hydroxyl group are known.
No. 1625, No. 51-30462, Japanese Unexamined Patent Publication No. 49-13
4326 and 49-134327, phenol and bisphenols, U.S. Pat.
No. 2 includes pyrogallol, gallic acid and its esters, U.S. Pat. Nos. 2,360,290 and 4,015,
No. 990 includes α-tocopherols and their acyl conductors, JP-B No. 52-27534, JP-A No. 52-147.
No. 51 and U.S. Pat. No. 2,735,765 contain hydroquinone rust conductors; U.S. Pat.
, 574,627, 5-hydroxychroman derivatives in U.S. Pat.
It has been proposed to use -dihydroxy-2,2'-subirobichromans and the like. However, although these compounds can be seen to some extent to be effective as dye fading and discoloration inhibitors, they are not sufficient.

British Patent No. 1,451,000 also describes improving the light stability of organic colored compounds using an azomethine quenching compound whose absorption peak is more bathochromic than that of the colored compound. However, since the azomethine quenching compound itself is colored, it has a large effect on the hue of the colored substance, which is disadvantageous. In addition, the use of metal complexes to prevent photodegradation of polymers has been reported in the Journal of Polymer Science, edited by Polymer Chemistry (J, Po
1yn+.

Sci., Polym, Chem, Ed.) Vol. 12, p. 993 (1974), Journal of Polymer Science, Polymer Letters IJ4 (J, Poly
m, Sci,, Po1ya+, Lett, Ed,)+
134J, p. 71 (1975), etc.
Furthermore, methods for stabilizing dyes against light using metal complexes are described in JP-A-50-87649 and Research Disclosure w-(Research Disclosure).
e) No. 15162 (1976), these complexes do not have a large anti-fading effect and do not have high solubility in organic solvents, so the amount of these complexes is sufficient to exhibit the anti-fading effect. cannot be added.

Furthermore, since these complexes themselves have a large coloring property, when added in large amounts, they have an adverse effect on the hue and purity of organic coloring substances, especially pigments.

Furthermore, methods for photostabilizing dyes using various metal complexes are disclosed in JP-A-54-62826, JP-A-54-62987, and JP-A-54.
-65185, 54-69580, 54-72
No. 780, No. 54-82384, No. 54-82385
No. 54-82386, No. 54-136581,
No. 54-136582, No. 55-12129, No. 5
No. 5-152750, No. 56-168652, No. 56
-167138, No. 57-16174, Special Publication No. 1987
-19770 etc.

However, even the above methods are still insufficient to reduce the coloration of the complex itself, and organic coloring substances,
In particular, the negative influence on the hue and purity of the pigment or dye cannot be eliminated.

Furthermore, when these known metal complexes are applied to silver halide color photographic materials (hereinafter referred to as color photographic materials), stains are likely to occur in uncolored areas of the developed color photographic materials. In particular, when a developed color photographic material is stored under conditions of high temperature and high humidity, the occurrence of contamination increases significantly.

Therefore, while researching the stability of color photographic images against light, the present inventor found that certain compounds not only have photostability on photographic images, but also have the photostability effect of a wide range of organic coloring substances. This discovery led to the present invention.

Object of the invention The object of the invention is to provide a method for improving the light stability of organic coloring substances.

Another object of the invention is to provide a method for improving the light stability of organic coloring substances, especially pigments or dyes, without deteriorating their hue and purity.

Yet another object of the present invention is to provide a method for improving the light stability of color images forming color photographic images without contaminating the uncolored areas of the color photographic material.

[Structure of the Invention] The above object of the present invention is to combine an organic coloring substance and the following general formula [I]
This is achieved by coexisting with at least 1 fffi of the compound represented by

General formula [1] [wherein R1 represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, or a heterocyclic group, 2. and z2 each have 2 carbon atoms
or represents 3 alkylene chains.

The present invention will be explained in more detail below.

In the above general formula [I], the alkyl group represented by R1 has 1 to 32 carbon atoms, the alkenyl group and alkynyl group have 2 to 32 carbon atoms, and the cycloalkyl group and cycloalkenyl group have 1 to 32 carbon atoms. 3-1
2, particularly those with 5 to 7 are preferred, and the alkyl group, alkenyl group and alkynyl group may be linear or branched. Moreover, these groups may have a substituent. in particular,
Methyl, ethyl, t-butyl, pentadecyl,! -hexylnonyl, 2-chloro-t-butyl, benzyl, 2.
Examples include groups such as 4-di-t-amylphenoxymethyl, 1-ethoxytridecyl, allyl, isopropenyl, ethynyl, 2-propynyl, cyclopentyl, cyclohexyl, and cyclohexenyl.

The aryl group represented by R1 is preferably a phenyl group or a naphthyl group, and may have a substituent.

Specifically, phenyl, 4-nitrophenyl, 4-t-
Butylphenyl, 2,4-di-t-amylphenyl, 3
Examples include groups such as -hexadecyloxyphenyl and α-naphthyl.

The heterocyclic group represented by R1 is preferably a 5- to 7-membered one, and may be substituted or fused.

Specific examples include 2-furyl group, 2-chenyl group, 2-pyrimidinyl group, and 2-benzothiazolyl group.

2, and 2. each represents an alkylene group having 2 or 3 carbon atoms, that is, an ethylene group or a straight propylene group,
These alkylene groups may have a substituent,
For example, representative examples include halogen atoms and alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, heterocycle, acyl, sulfonyl, phosphonyl, carbamoyl, sulfamoyl, cyano, hydroxyl, alkoxy, aryloxy, heterocycleoxy, Examples include acyloxy, carbamoyloxy, amino, acylamino, sulfonamide, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, and aryloxycarbonyl groups.

In the present invention, n of the compound represented by general formula [I]
It is particularly preferred when l is an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group.

Next, typical examples of the compound represented by the general formula [I] used in the present invention will be shown, but the present invention is not limited thereto.

The following is a blank general formula [1-a] General formula CI-al (Continued) (The following is a blank) General formula [I-bl A-23A-24 These compounds used in the present invention are known, for example, as described in the Journal of Heterogeneous Cyclic Chemistry (J, 1 (eterocycle, Chew,)
It can be synthesized according to the synthesis method described in 19B4゜21(1), pages 37-39.

The amount of the compound used in the present invention is preferably 5 to 400 mol%, more preferably 10 to 300 mol%, based on the organic coloring substance used in the invention.

The organic coloring substances used in the present invention include basic dyes, acid dyes, direct dyes, soluble vat dyes, water-soluble dyes such as mordant dyes, sulfur dyes, vat dyes, oil-soluble dyes, disperse dyes, azoic dyes, It includes all dyes belonging to the classification of dyeing properties such as insoluble dyes such as oxidative dyes or reactive dyes.

These organic coloring substances were mixed with 300n in methanol solution.
m to 8oons, preferably 400nm to 700
It has at least one absorption maximum at n11.

Among these dyes, the dyes preferably used in the present invention include quinone imine dyes (azine dyes, oxazine dyes, thiazine dyes, etc.), methine and polymethine dyes (cyanine dyes, azomethine dyes, etc.), azo dyes, anthraquinone dyes, indoamine dyes, and It includes dyes belonging to chemical structural classes such as indophenol dyes, indigoid dyes, carbonium dyes, and formazan dyes.

The organic coloring substance used in the present invention is an image-forming dye used in the field of photography, such as color coupler, DRR.
It includes all dyes formed from compounds, DDR couplers, amitracine compound dye developers, dyes for silver dye bleaching methods, etc.

Preferred dyes for use as organic colorants of the present invention include anthraquinone, quinone imine, azo, methine,
These include polymethine, indoamine, indophenol and formazan dyes. The dyes most preferably used in the present invention are methine and polymethine dyes and indoamine and indophenol dyes. This dye includes compounds having the following groups.

Among the above groups, the phenyl group represents an unsubstituted phenyl group or a substituted phenyl group, such as a phenyl group substituted with an alkyl group, an alkoxy group, a halogen atom, an amino group, or the like.

Dye-forming couplers suitable for use in this invention include yellow, magenta and cyan dye-forming types. This coupler is described in US Pat. No. 3,277.155, for example.
The so-called 4-equivalent type as described in No. 3,458,315, or the carbon atom at the coupling position is substituted with a substituent that can be separated during the coupling reaction (split-off group). It may also be a 2-equivalent type.

Preferred examples of yellow dye image-forming couplers in the present invention include benzoylacetanilide-type and pivaloylacetanilide-type couplers, and examples of magenta dye-image-forming couplers include 5-pyrazolones, pyrazolotriazoles, imidazopyrazoles, and pyrazolopyrazoles. system,
There are pyrazolotetrazole-based, pyrazolinobenzimidazole-based, and indasilone-based couplers, and cyan dye image-forming couplers include phenol-based, naphthol-based, and pyrazoloquinazolone-based couplers.

Specific examples of these yellow, magenta, and cyan dye-forming couplers are known in the photographic industry, and the present invention encompasses all of these known couplers.

Next, typical examples of yellow couplers that can be used in the present invention are listed.

The following margin rI Q Q rσ rθ rσ These yellow couplers can be used, for example, in
No. 057,941, West German Published Patent No. 2,163,812, Japanese Patent Application Publication No. 47-26133, Japanese Patent Publication No. 4B-29432,
No. 50-65321, No. 51-3631, No. 51-
No. 50734, No. 51-102636, No. 4B-66
No. 835, No. 48-94432, No. 49-1229, No. 49-10736, Special Publication No. 51-33410,
It includes the compounds described in No. 52-25733 and the like, and can be synthesized according to the methods described therein.

Next, typical examples of magenta couplers that can be used in the present invention will be listed.

I I CI Js M-6 These magenta couplers are described, for example, in U.S. Pat.
No. 4,514, British Patent No. 1,183,515, Japanese Patent Publication No. 40-6031, No. 40-6035, No. 44-15
No. 754, No. 45-40757, No. 46-19032
No., JP-A-50-13041, JP-A No. 53-129035
No. 51-37646, No. 55-62454, U.S. Patent No. 3,725,067, British Patent No. 1,252
, No. 418, 1.

334, No. 515, JP-A No. 59-171956, No. 5
No. 9-162548, No. 60-43659, No. 60-
No. 33552, Research Disclosure No. 2
4626 (1984), Japanese Patent Application No. 59-243007, No. 59-243008, No. 59-243009,
No. 59-243012, No. 60-70197, No. 8
0-70198, etc., and can be synthesized according to the methods described therein.

Although there are no particular limitations on the cyan coupler used in the present invention, a phenolic cyan coupler is preferred.

Next, typical examples of cyan couplers that can be used in the present invention will be given.

C.I. C.I. C.I. C-5 C, I+.

These cyan couplers are described, for example, in U.S. Pat.
．． No. 730, No. 2,801,171, Japanese Unexamined Patent Publication No. 1973-1
No. 12038, No. 50-134644, No. 53-10
No. 9630, No. 54-55380, No. 56-6513
4, No. 56-80045, No. 57-155538, No. 57-204545, No. 58-98731, No. 59-31953, etc., and methods described therein. 0 which can be synthesized according to
When such couplers are used in the present invention, dyes are formed from these couplers by reaction with an oxidized aromatic primary amine silver halide developer.

The above developers include amine phenol and phenylene diamine, and these developers can be used in combination.

Representative examples of developers that can be combined with various couplers to form colored compounds in accordance with the present invention are listed below.

[Example developer]

D-I D-2 D-3D-4 D-5D-13 Examples of other dyes that can be used as coloring compounds in the present invention include the following.

i1 NJISO, CI et al. Further, other types of dyes preferably used in the present invention include U, S, B551,673, U.S. Pat.
, No. 381, No. 3,928.312, No. 3,931,
No. 144, No. 3,954.478, No. 3,929,7
No. 80', No. 3,942,987, No. 3,932,3
No. 80, No. 4,013,635, No. 4,013,63
No. 3, JP-A-51-113624, JP-A No. 51-1099
No. 28, No. 51-104343, No. 52-4819, No. 53-149328, Research Disclosure w-No. 15157 (1976) No. 13
Examples include dyes formed by oxidation of DRR compounds described in, for example, 024 (1975). Furthermore, other types of dyes which may be used in the present invention include, for example, British Patent Nos. 840.731, 904.364, 932,272, 1.014.725, 1.0
38゜331, 1,066.352, 1,09
No. 7,064, JP-A-51-133021, IJsT
900.029 (υ, 5. DefensiveP
U.S. Pat. No. 3,227,550
Mention may be made of dyes released by the reaction of DDR couplers such as those described in No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, 2010-12, and dyes released by the reaction of DDR couplers with oxidized products of color developing agents, or dyes formed by the reaction of DDR couplers with oxidized products of color developing agents.

Other types of dyes preferably used in the present invention include Japanese Patent Publications No. 35-1112, No. 111:132, No. 48-32130, No. 46-43950, No. 49-
Examples include dye developers described in No. 2618 and the like.

Furthermore, other dyes used in the present invention include various dyes used in silver dye bleaching methods. Yellow dyes that can be used for this purpose include Direct Fast Yellow GC (C, 1,29000),
Azo dyes such as glisophenine (C, 1,24895), indigo golden yellow IGK (C, 1,59
101), Indigosol Yellow 2GB (C, 1,
61726), Arbosol Yellow〇C^-CF(
C, 1,67301), indanthrene yellow GF
(C, 1°68420), Mikethrene Yellow GC (
C, 1,67300), benzoquinone dyes such as Indanthrene Yellow 46 (C, 1,68405); anthraquinone dyes, polycyclic soluble vat dyes, and other vat dyes. As a magenta dye, Sumilite Subralbinol B (C,!, 292
25), penzobrilliant keranin B (C,1,
15080), Indigosol Brilliant Pink IR (C, 1°73361), Indigosol Violet 15R (C, I.

59321), Indigosol Red Violet IR
RL (C, 159316), Indanthrene Red Violet RR (C, 1,67895), Mikethrene Brilliant Violet BB (C, 1,6335)
) and other indigoid dyes; soluble vat dyes consisting of benzoquinone and anthraquinone heteropolycyclic compounds;
Other vat dyes may be mentioned.

As a cyan dye, Direct Sky Blue 68 (
C,1,24410), Direct Brilliant Blue 28 (C,1,22610), Sumilight Subra Blue-G (C,1,34200), etc., Sumilight Subra Turkey Blue G (C,1,74180)
), Migaslen Brilliant Blue 4G (C, 1, 7
phthalocyanine dyes such as Indanthlen Turkey Sprue 5G (C, 169845), Indanthrenblue-GCD (C, 1°73066), Indigosol 04G (C, 1,73046), Anthrazol Green IB (C, , 1,591126).

The compounds of the present invention are generally oil-soluble and are typically used in U.S. Pat.
．． According to the methods described in No. 801.171, No. 2,272,191 and No. 2,304゜940, it is dissolved and dispersed in a high boiling point solvent and, if necessary, a low boiling point solvent. It is preferable to add it to a colloidal solution, and at this time, if necessary, a coupler, a hydroquinone derivative, an ultraviolet absorber, a known dye image fading inhibitor, etc. may be used in combination without any problem. At this time, there is no problem even if two or more of the compounds of the present invention are used as a mixture. To further explain in detail the method of adding the compound of the present invention, 1 f! i or two or more of these compounds, if necessary, and a coupler, a hydroquinone derivative, an ultraviolet absorber, or a known dye image fading inhibitor, etc. at the same time as organic acid amides, carbamates, esters, ketones, hydrocarbons, etc. and urea derivatives, etc., especially dibutyl phthalate, tricresyl phosphate, Jimmy octyl azelate, dibutyl sebacate, trihexyl phosphate, decalin, N,N-diethylcaprylamide, N,N-diethyllaurylamide, pentadecyl Add ethyl acetate, butyl acetate, butyl propionate, cyclohexanol, or
These high boiling point solvents and low boiling point solvents which are soluble in low boiling point solvents such as cyclohexane and tetrahydrofuran may be used alone or in combination. ) Mixed with an aqueous solution containing a wood-philic binder such as gelatin containing anionic surfactants such as alkylbenzenesulfonic acids and alkylnaphthalenesulfonic acids and/or nonionic surfactants such as sorbitan sesquioleate and sorbitan monolaurate. Then, it can be emulsified and dispersed using a high-speed rotating mixer, a colloid mill, an ultrasonic dispersion device, etc., and the resulting dispersion can be added to a hydrophilic colloid solution (for example, a silver halide emulsion) for use.

Both the colorant and the compounds of this invention can be present in any or several of the parent colloid layers in the photographic element. These materials may be present in light-sensitive elements and non-light-sensitive elements such as dye image receptors used in photographic diffusion transfer film units. When included in a photosensitive image recording element, they are preferably mordanted. Therefore, for such uses, the compounds of the present invention have a molecular form that allows them to be retained in the mordant layer of the image receptor so that they do not migrate away from the dye to be stabilized. must be maintained.

In the photographic light-sensitive material used in the method of the present invention, the silver halide emulsion is generally one in which silver halide grains are dispersed in a wood-philic colloid, and the silver halide includes silver chloride, silver bromide, and silver iodide. , silver chlorobromide, silver iodobromide, silver chloroiodobromide and mixtures thereof.

These silver halide emulsions can be optically sensitized using various sensitizing dyes in order to impart photosensitivity in a desired wavelength range. Further, chemical sensitization can be carried out by a conventional method in the field of photography.

Silver halide emulsions are known as antifoggants or stabilizers in the photographic industry for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, and/or keeping photographic performance stable. Compounds that are present can be added.

In addition, various photographic additives such as hardeners, plasticizers, optical brighteners, antistatic agents, and coating aids may be used alone or in combination.
More than one species can be added and used in combination.

The color photographic material to which the present invention is applied may be a coupler-containing internal color photographic material or an external color photographic material containing a coupler in a developer.

The above-mentioned coupler-containing internal color photographic material is processed in a conventional manner to obtain a color image. The main steps in this case are color development, bleaching, and fixing, and if necessary, steps such as washing with water and stabilization may be included. Two or more of these steps, such as bleach-fixing, can be carried out in one bath. Color development is usually carried out in an alkaline solution containing an aromatic primary amine developing agent. Preferred specific examples of these aromatic primary amine developing agents are described above as exemplified developers D-1 to D-6.

When the color photographic material to which the method of the invention is applied is a film unit for color diffusion transfer, processing of the photographic material takes place automatically within the light-sensitive material. In this case, the developing agent is contained in a rupturable container. As the developing agent, in addition to the compounds represented by D-1 to D-6 above,
N-methylaminophenol, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-hydroxyf-3-pyrazolidone, 3-methoxy-N,N -diethyl-p-phenylenediamine, etc. can be used.

When applying the method of the present invention to photographic materials, various color photographic materials such as color positive film, color paper, color negative film, color reversal film, color diffusion transfer film unit, and silver dye bleaching material may be used. It will be done.

[Examples] The present invention will be described below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 0.5 g of magenta dye having the following structure (absorption maximum in methanol solution: 538 nm) was mixed with 4 m of trioctyl phosphate. ! and 8mp of ethyl acetate, and this solution was mixed with 0.5% aqueous sodium dodecylbenzenesulfonate solution 2raI! was emulsified and dispersed in 10 m2 of a 10% gelatin solution containing

Next, this emulsified dispersion was mixed with 30mj> of a 5% gelatin solution and coated on a paper support laminated on both sides with polyethylene to obtain a sample. This sample is designated as No.1.

When preparing the above emulsified dispersion in a similar manner, comparative compounds represented by the following structural formulas (a) and (b) were each added at 0%
．． 5g was added and coated in the same manner as Sample No. 1 above to prepare Samples No. 2 and No. 003.

Further, when preparing the emulsified dispersion liquid by the method of the above sample No. 1, 0.5 g of each of the exemplary compounds of the present invention was added as shown in Table 1 and applied in the same manner as the above sample No. 1. 12M1 samples (No. 4 to 15) were prepared.

Comparative compound (a)... Gold yA complex comparative compound (b) described in JP-A No. 55-12129... Same as above Each of the above samples was exposed to a xenon fade meter for 200 hours, and the light resistance of the dye image was determined. I looked into gender. The results are shown in Table 1. However, the light resistance of the dye image was determined based on the dye residual rate.

As is clear from Table 1, the samples (Nos. 4 to 15) using the anti-fade agent of the present invention have a better photo-fade prevention effect than the samples (Nos. 2 and 3) using known metal complexes. Moreover, almost no blackish-brown discoloration was observed.

Example 2 In Example 1, the magenta dye was used as a magenta dye having the following structure (maximum absorption of 536 nm in methanol solution).
15 in the same manner as in Example 1 except that
Rice samples (No. 16 to 30) were prepared.

The obtained sample was exposed to a xenon fade meter for 150 hours to examine the light resistance of the dye image. The results are shown in Table 2.

(Magenta Dye) Table 2 Table 2 also shows that the sample using the anti-fading agent of the present invention has a superior photo-fading preventing effect than the sample using the known metal complex. In addition, the sample according to the present invention showed almost no blackish-brown discoloration and maintained a favorable hue even after the light fastness test.

Example 3 Example coupler (M-8) 30g as magenta coupler
A solution of 30 mj of triphenyl phosphate and 100 mj of ethyl acetate was added to 500 mj of a 5% aqueous gelatin solution containing 2.5 g of sodium dodecylbenzenesulfonate.
IIli), then dispersed with a homogenizer, and the resulting dispersion was added to green photosensitive silver chlorobromide (30 mol% silver chloride).
(containing) emulsion t, ooo- and N as a hardening agent.
,N',N''-triacryloylhexahydro-S-
10 mp of a 2% methanol solution of triazine was added, coated on polyethylene coated paper and dried to obtain a sample of a monochromatic color photographic material. This sample is designated as No. 31.

Samples No. 32 and No. J3 were prepared by adding 24 g of each of comparative compounds (C) and (d) having the following structures to the same method to prepare the above emulsified dispersion.

Furthermore, as shown in Table 3, 20g of each of the exemplary compounds of the present invention was added and applied in the same manner to prepare seven samples (No. 34).
-40) were created.

Comparative compound (c)... Compound described in JP-A No. 54-48538 Comparative compound (d)... Compound described in JP-A-56-159644 After each of these samples was exposed, the following treatment was performed. Processed with liquid and processing steps.

[Developer] Benzyl alcohol 12.0ml!
Sodium hexametaphosphate 2.5g Anhydrous sodium sulfite 1.9g Sodium bromide 1.4g Potassium bromide 0.5g Sodium carbonate
30.0gN-ethyl-N-β-
Methanesulfonamidoethyl-4-aminoaniline sulfate 5.0g Add water to obtain Ik, and adjust to pH 10.30 using sodium hydroxide.

[Bleach-fix solution] Iron ammonium ethylenediaminetetraacetate 61.0g Diammonium ethylenediaminetetraacetate 5.0g Ammonium thiosulfate 124.5g Ammonium metabisulfite 13.3g Anhydrous sodium sulfite 2.7g Add water to make 11, and use aqueous ammonia. Adjust the pH to 6.5.

[Processing process] (30℃) Processing time Development 3 minutes 30 seconds Bleach fixing 1 minute 30 seconds Washing with water 3 minutes drying Each sample with a dye image formed in this way was coated with Kodak Latte, an ultraviolet cut filter. filter N
o, 15 [1 with a xenon fade meter with 2A attached.
A time fading test was conducted. The results are shown in Table 3.

The degree of fading was indicated by the change in density of the 1.0 density portion before the fading test.

Table 3 (The absorption maximum of the colored magenta dye in methanol solution was 536 nI11.) As is clear from the results in Table 3, the anti-fading agent of the present invention has superior photofading properties to conventional organic anti-fading agents. It has a preventive effect.

Example 4 As a cyan coupler, 35 g of the exemplary coupler (C-6) was mixed with 35 mj of dioctyl phthalate and 100 g of ethyl acetate.
n+i) was added to a 5% gelatin aqueous solution SOO containing 2.58% sodium dodecylbenzenesulfonate.
mj), then dispersed with a homogenizer, and the resulting dispersion was added to a red photosensitive silver bromide (containing 30 mol% silver chloride) emulsion 1,000-, and N, N', N, N',
10 mJ of a 2% methanol solution of N'-triacryloylhexahydro-S-triazine was added, coated on polyethylene coated paper and dried to obtain a sample of a monochromatic color photographic material. This sample is designated as No. 41.

When preparing the emulsified dispersion liquid in the same manner as in Example 3, 15 g of each of the comparative compound (e) having the following structure and the exemplified compound of the present invention as shown in Table 4 were added to prepare 9 types of samples (No. 4).
2-50) were created.

Comparative compound (e): Compound described in JP-A No. 59-87458 After exposing each of these samples, the dye image obtained by processing in exactly the same manner as in Example 3 was filtered with an ultraviolet cut filter ( A 250 hour fading test was carried out using a xenon fade meter with the same material as used in Example 3). The results are shown in Table 4.

(The absorption maximum of the colored cyan dye in methanol solution is 6
It was 52 nm. ) As is clear from Table 4, the anti-fading agent of the present invention also has a large effect of preventing photofading of cyan coloring dyes.

Example 5 Next, an example in which the present invention is applied to a heat-developable photosensitive material will be shown.

<Preparation of heat-developable photosensitive elements> Heat-developable photosensitive elements shown in Table 5 were prepared using the following materials.

Gelatin: Photographic lime-processed gelatin and phenylcarbamoylated gelatin (manufactured by Rousslow, type 17819)
PC) mixed at a ratio of 2:1 (weight ratio).

PvP...Polyvinylpyrrolidone (ni-30) solid heat solvent...p-butoxybenzamide liquid heat solvent...
1.2.4-Butanetriol reducing agent: A mixture of the following reducing agents A and B at a molar ratio of 7=3.

(A) Organic silver salt: 5-methylbenzotriazole Silver photosensitive silver halide: The same salt as described in the Examples of Japanese Patent Application No. 61-254257 was used.

Yellow dye donor @ (Y-CPM) x:y:÷=8
〇220 (TL weight ratio Magenta dye-providing substance (M-CPM) x:y = 40:60 (weight ratio) Cyan dye-providing substance (C-CPM) 1tl x:y=60:40 (weight ratio) Table 5 The unit is gets' (however, organic silver salt and photosensitive A
( g
m'), apply the following image-receiving layer coating solution to a wet film thickness of 137.2 mm.
A heat-developable image-receiving element was prepared by coating with a thickness of μm and drying (Sample No. 51).

(Image-receiving layer coating liquid) Polyvinyl chloride (manufactured by Wako Pure Chemical Industries, Ltd., n = 1,100)
21.0g Tetrahydrofuran 190 mj)
When preparing the above image-receiving layer coating solution in the same manner, as shown in Table 6, add 0.8 g each of the comparative compound, ultraviolet absorber, and exemplified compound of the present invention (0.4 g if used together).
In addition, nine types of samples (Nos. 52 to 60) were prepared by coating in the same manner as Sample No. 51 above.

The heat-developable photosensitive element was exposed to 4000 CMS of tungsten light through a step wedge and a green filter, and the coated surfaces of the heat-developable image-receiving element were overlapped with each other and preheated at 100° C. for 4 seconds.
Pressure heating (thermal development) was performed at ℃ for 90 seconds. In addition,
Preheating and compression heating were carried out using a heat developing apparatus shown in FIG. 2 of JP-A-81-153651.

After the heating was completed, the image receiving element was quickly peeled off from the photosensitive element, and a magenta image was obtained on the surface of the image receiving element. The photographic properties and light stability of this color image were investigated. The results are also shown in Table 6.

(Evaluation of photographic characteristics) The maximum reflection density and minimum reflection density of the magenta image were measured using a Sakura densitometer PDA-[i5 (manufactured by Konishiroku Photo Industry).
Measured using green light.

<Evaluation of edge resistance stability> A sample with a magenta image was irradiated with light for 5 and 10 days using a xenon fade meter (Suga Test Instruments WE-6X-HC), and the dye concentration residual rate (%) was examined. .

Table 6 Medium outer radiation absorber (UV-1) The middle comparative compound (C) is the same as that used in Example 3.

Table 6 shows that even when the anti-fading agent of the present invention is used in heat-developable photosensitive materials, it exhibits an excellent anti-fading effect without impairing photographic properties. Further, by using the anti-fading agent of the present invention and an ultraviolet absorber together, the anti-fading effect is further improved.

[Effects of the Invention] By allowing the photofading inhibitor according to the present invention to exist together with an organic coloring substance, it is possible to significantly reduce the fading of organic coloring substances, especially pigments, dyes, etc. used in color photographic materials due to light. can.

Claims (1)

[Claims] Photofading of an organic coloring substance, characterized in that fading of the organic coloring substance against light is prevented by coexisting the organic coloring substance and at least one compound represented by the general formula [I]. How to prevent it. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. and Z_2 each represent an alkylene chain having 2 or 3 carbon atoms. ]